Arylamides of meta-hydroxy-diarylamine-carboxylic acids and process of making same



Fatented 11, 1932 UNITED {STATES LEOPOLD LASKA enn osimn HALLER, or 1waaamca maamm, eaaaaar,

ASSZGNOBS TO GENERAL ANILI-NE won xs, INC., on NEw sroR-K, N. Y, A summation.

OF DELAWARE ARYLAMIDES or 1aETA-HYDRQXY D ARYLMarita-cartsoXYLic Acrns AND PRooE'ss 1 on Y MAKING jsAr'aE No Drawing. Application filed Jui a, 1930 Serial No. 465,780, and in Germany July 17, 1929.

eral formula (wherein one X means hydrogen, the other X methyl and the benzene nucleus signified by I may contain further substituents) and toa process of making same. I

The process being object of the present invention comprises condensing in the presence of an acid condensing agent a meta-hydroxydiarylamine carboxylic acid of the probable general formula: 1

@eNHQ -COOH.

(wherein and the nucleus have the aforel saidsignification), which acids are described in U. S. application Ser. No. 464,830, filed June 27, 1930, with a primary aromatic amine, whereto a diluent may be admixed.

The new arylamides being object vof the present invention are, like. the products of U. S. application Serial No.' 430,130, filed February 20, 1930, distinguished by a great afiinity to the vegetable fiber. The quantity of these arylamides which is fixed on cotton 5 from-an alkaline solution of equal concentration, is many times that of the corresponding arylamides of cretontinic acid. From this reason they represent valuable intermediates for the production of dyestuffs.

In orderto further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrad'e degrees, but we wish it however to be understood that we are not limited to the particular products nor reaction conditions mentioned therein z' Example 1 i 48f6 parts of 3-hydroxy-fi-methyl diphenyl amine-carboxyli'c acid are added with 20 parts of aniline to 500 parts of o-dichlorobenzene. At 7 080 12 parts of phosphorus eral hours at 100 until the condensation is finished. The reaction mass is made alkaline with a solution of sodium carbonate, the

' dichloi'o-benz'ene is blown away by means of steam and the formed anilide of the 3- hydroxy 4 6 methyl-diphei1ylaniine-4L'-carboxylic acid isfiltere'd, It may be purified by dissolving it in a caustic'soda solution and by precipitating with carbonic acid. When recrystallized from xylene the new anilide of the probable formula 51.4 parts of phenylamine-4-ca'rboxylic acid are introduced with 20 parts of aniline into 500part s of o-dichloro benzene and at a temperature" of 7 080 12 parts of phosphorus trichloride are added to the mixture; The reaction mass is further treated and Worked up as described in Example 1. The formed anilide of the 3- hydroxy-6A-dimethyl-diphenylamine4-carboxylic acid may be purified by dissolving it in a caustic soda solution and by precipitating with carbonic acid. When recrystallized from xylene the new anilide of the probable formula: V

melts at 219 7 Example '3 24. 3 jp'a rts of 3-hydroxy-6-methyl-diphenylamine--carboxylic acid are addedwith 1328 parts of p-nitroan-iline to 1000 parts of toluene andat a temperature of TO- 80 '6 parts of phosphorus 'trichlo'ride are allowed 3t amXy-Ba aimethyiet r to run in slowly. The temperature is mainmelts 225. i

tained for several hours at 110 until the condensation is finished. The reaction mass is rendered alkaline with a solution of: sodium carbonate, the toluene is blown away by means of steam and the formed p-nitro-anilide of the 3-hydroXy-6-methyl-diphenylam ine-4 carboxylic acid is filteredofi. It may be purified" by dissolving it in a caustic a lkali lye and precipitating with carbonic acid. WVhenrecrystallized from o-dichlorobenzene the new p-nitro-anilide' of theprobable formula:

Exe plarf x 48.6 parts of 3-liydroxy-6-methyl-diphenylamine-4-carboxylic acid and 21.4 parts' of p-toluidine are introduced into 750 parts of dimethyl-aniline and at 7080 12 parts of phosphorus trichloride I are added gradually to the mixture. The temperature is kept for several hours at 100. When thecondensation is finished the reaction massis introduced into diluted hydrochlorid acid," the precipitate is filtered. 0E, made alkaline with a solution of sodium carbonate and if freed ,from dimethyl-an'iline by means of y the o-anisidide of the 3-hydroxy-6.4, -dimeth yl-diphenylamine-4-carboxylic acid thus obprobably to the following formula:

The corresponding p-chloro-anilide melts, when recrystallized from xylene, at 186;

the corresponding p-anisidide melts, when recrystallized from Xylene,at 180 when recrystallized from benzene, the corresponding o-anisidide melts at 152.

Example-5 To a-mixture of 51.4 parts of 3-hydroxy- 6.4 dimethyl diphenylamine-t-carboxylic acid and 24.6 parts of o-anisidine-1'100 parts of toluene are added and at 7 O-80 l2 parts of phosphorus trichloride'are allowed to run in gradually. The reaction mass is further treated andv worked up as described in -EX-" ample 3. ,When recrystallized from benzene tained, which corresponds probably to the following formula: a

. on r moNi1:-oo- H 3 if .7 Tom 2 on; v

gmelts at 150 151. g V

i i Ewampled Into a' mi xture 0f 51.4 parts of S-hydroxy- 6.4 dimethyldiphenylamine 4-carboxylic acid and 25.4 parts of p-chloro-aniline 7 50 parts of dimethyl-aniline are introduced- At a temperature of 80 12 parts of phosphorus trichlorides are allowed to run in gradually. The reaction mass is further I treated and worked up as described in Exam ple 4." When recrystallized from Xylene the I. "p-chloro-anilide of the 3 hydroXy-6.4-dimethyl-diphenylamine-4-carboxylic acid thus obtained ofthe probable formula;

melts at 203204.

The corresponding p-nitro-a'nilide nielts when recrystallized from o-di'chloro-benze'ne at'208. When recrystallized from Xylene the corresponding B-naphthylamide melts at I Example 7 m Toa mixture of 27.7 5 parts of 3-hydroxy- 6-methyl-4-chloro diphenylamine 4- carboxylic'acid, 10 parts of aniline and 1100 parts of Xylene at a temperature of 7 080 6 parts of phosphorus trichloride are gradually added to the whole is further treated and worked up as described in Example. 3. The

' anilideof the 3-hydroXy-6-methyl-4 chlorodiphenylamine-4-carboxylic acid thus obtained melts when recrystallized from chloro-.

benzene at 183 and corresponds probably to the following formula: I 1."- fi I MQ H gQ-OHSV It.

Example 8 27.75 parts of -3-hydroXy-6 -methyl-4'- chloro-diphenylamine-4 carboxylic acid and 14.3 parts offi-naphthylamine. are introduced into 750 parts of dimethyl-aniline and at a temperature of 7 080' 6 parts .of phosphorus trichlorideare added gradually to themixture. The reaction mass is worked up in thesame manner as described in 'EXL ample 4 or 6. When-recrystallized from xylene the ,B-naphthylamide ofthe 3-hydroxy- -6methyl 4r chloro diphenylamine-4- nylaminel-carboxylic acid and 13.8 parts of p-nitro-aniline 1000 parts of toluene are addcarboxylic acid thus obtained of the probable formula. v

i on

Q QMH 0H8 1 V I V melts at 211.

Example 9 To a mixture of 29.95 parts of the sodium salt of 3-hydroxy-6-methyl lchloro-dipheed and at 80 6 parts of phosphorus trich loride are allowed to run in slowly. The temperature is kept for several hours at 110.

WVhen the condensation is finished the reaction mass is worked up as described in Example 3. The p-nitro-anilide of the 3-hydroxy-6-methyl-4'-chloro-diphenylamine-4-carboxylic acid thus obtained corresponds probably to the formula:

WVhen recrystallized from nitrobenzene it melts at 255.

l Vhen recrystallized from xylene the corresponding: p-chloro-anilide metals at 203, panisidide melts at 17 8 o-toluidide melts at 185, o-anisidide melts at 158- The corresponding m-nitro-anilide melts, when recrystallized from o-diohloro-benzene, at 231.

E wample 10 on N01 melts when recrystallized from xylene at 145.

Example 11 55.5 parts of 3-hydroxy-5-methyl-4-chlorodiphenylamine-4L-carboxylic acid and 20 parts of aniline are added to 1000 parts of chlorobenzene. At 7 0-80", 12 parts of phosphorus trichloride are allowed to run into the mixture and the temperature is then maintained at 110 for several hours until the condensation is finished. The reaction mass is worked up as described in Examplel. The anilide of the 3- hydroxy-5-methyl-4-chloro-diphenylamine-i-carboxylic acid thus obtained corresponds 'probablyto the following for mula s oIONH C -OONHO VVhen recrystallized from xylene the corresponding p-chloro-anilide melts at 159 and the corresponding fi-naphthylamide at 168.

1. Process which comprises condensing in the presence of phosphorous trichloride a 3- hydroxy-diarylaminel-carboxylic acid of the probable general formula:

(wherein one X means hydrogen, the other X methyl and the benzene nucleus signified by I may contain alkyl or halogen), with a primary aromatic amine, whereto a diluent may he admixed. Y

2. Process which comprises condensing in the presence of phosphorous trichloride a 3-hydroxy-diarylamineel-carboxylic acid or the probable general formula:

(wherein one X means hydrogen, the other X methyl and Y alkyl or halogen), with a primary aromatic amine, whereto a diluent. may be' admixed. i v

8.-Process which comprises condensing in the presence of phosphorous trichloride a 3-hydroxy-diarylaminel carboxylic acid of the probable general formula: 2

Y-ONH-Q-COOH (wherein one Xmeans hydrogen, the other X methyl and Y alkyl or halogen) with it-nitroaniline, whereto a diluent may be admixed.

. 4. As new compounds the arylamides of 3-hydroxy-diarylamine 4 carboxylic acids corresponding to the probable general formula:

(wherein one X means hydrogen, the other X methyl and the benzene nucleus signifiedby I 9 mula may contain'alkylfor halogen) which compounds are armorphous or crystallized substances, having-a definltemelting point, diffi cultly soluble in organic solvents, -easily niethyl andY' alkyl or halogen), which compounds are amorphous or crystallized substances, having a definite melting point,

diliieultly soluble in organic solvents, easily soluble in alkalies,"distinguished by a great,

affinity to the vegetable fiber.

6. As new compounds the arylamides of -'corresponding probably to the general formula;

filntestimony whereof, we aifix our signav tures. (wherein one X means hydrogen, the other X 7 r 3-hydroxy-diarylainine -carboXylic a ci d s which compound is 'difiicultly soluble inorganic solvents, easily soluble in alkaliesand melts when recrystallized from Xylene iat T LEoPoLD- LAsKiiI OSKAR HALLER. ,Y

(wherein one X meansl -hydrogen, theother X methyl and Y alkyl or halogen), which 3 compounds are ainorphous, or crystallized 'substances, having a definite melting point, difiicultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great affinity to the vegetable fiber. y

7 As a new compound, the para-chloro- 40: anilide of the S-hydroxy-GAJ-diinethyl-dip I phenylamine--carboxylic. acid correspond-- j ing to the probable formula:

': V V C I H30 NH CO NH Cl anilide of the 3 hydroxy-6-1nethyl-4Zchlorodiphenyla-mine ecarbonylic acid correspondingto'the probable formula:

..on I

which compound is diflicultly soluble-in organic solvents, easily soluble in alkalies and melts when recrystallized from nitrobenzene flat 255, i 1 

